Asphalt emulsion



P 1962 .1. R. WRIGHT ETAL 3,052,639

ASPIIALT EMULSION Filed Sept. 25. 1957 IIIIIII I I DEMULSIBILITY I I I I I I 0.40 0.50 0.60 POLYGLYCOI. ESTER. PER GENT +v1scosmr (0.155 PER GENT KOH) I I I I I I 0 oo o o o o 0 en 0 In .r m m INVENTORS JAMES R. WR/GH7 EDWARD W. MERTENS United. States Patent C)fice 3,052639 Patented Sept. 4, 1962 3,052,639 ASPI-IALT EMULSION James R. Wright and Edward W. Mertens, EI Cerrito, Calif., assignors to California Research Corporation, San Francisco, Calif. a corporation of Delaware Filed Sept. 25, 1957, Set. N0. 686,087 2 Claims. (Cl. 252311.5)

Ths invention relates to a new and improved asphalt emulsion. More particularly, the invention concerned with high residue anionic asphalt emulsions having improved viscosity characteristics.

Asphalt, or bitumen as it is also called, is useful in a wide variety of applications. Illustrative applications mclude its use in the paving of road surfaces, waterproof coatings and protective coatings in general, as well as the im rgnation of fiber-containing materials such as paper or e t.

Generally speaking, asphalt is employed in applications of the above type mainly in three forms of liquids. In perhaps its oldest form it is melted by heating and applied as a molten mass. It it also combined with volatile organic solvents to provide liquid solutions of desired viscosity known as cutbao asphalts. Asphalt is also emulsiied with water and used in the form of liquid asphalt emulsions. Ths last form, to which the present invention relates, has several advantages over molten asphalt and out-back formulations. The asphalt is maintained in liquid form during application without the need for expensive fheating equipment and at the same time the high oost and fire hazards involved in the use of organic solvent are avoided.

Asphalt emulsions are usually prepared by mixing the asphalt with an aqueous solution of an alkali metal hydroxide such as sodium or potassium hydroxide to saponify certain high molecular weght carboxylic acids in the asphalt. Such acids may occur naturally in the asphalt or they may be added where the natural acid content is unsatisfactorily W. The soaps thus formed serve as emulsifying agents to produce asphalt emulsions when the asphalt and water of the aqueous solution are mixed together. These asphalt emulsions are classified as anionic in nature because the aI-kali metal soap emulsifying agents bear a negative charge and are attracted to the anode or positive pole in solut-ion.

A number of special properties are desirable in the socalled quiok breaking asphalt emulsions of the present type. One of the most important and fundamental properties is a low viscosity in combination with a high residue. Snce asphalt emulsions are usually applied by machinery, it is important that the emulsion flows free- 1y. Low viscosity emulsions are also usually more penetrating and, therefore, more eective in the usual coat ing and mpregnating applications. It is particularly desirable that a high residue be maintained where possible along with the 10W viscosity of the asphalt emulson in order to avoid the necessity for handling unduly large amounts of emulsion in a given application. The stabilies of asphalt emulsions -are also important factors because it is highly desirable that separation of the asphalt and aqueous phases and increased viscosities be avoided when the emulsions are allowed to stand as during storage. At the same time, it is essential that the emulsion separate rapidly on contact with the matenial to be coated or impregnated such as aggregate, feit and paper. Suitable asphalt emulsions should likewise quickly demulsify in the presence of electrolytes such as calcium chloride.

It has now been found that a greatly improved high residue asphalt emulsion of 10W viscosity is obtained in the composition comprising a.n anionic asphalt emulsion and fiom 0.05 te 2.0 percent by weight of polyethylene glycol monoester of fatty acid having from 2 to 75 ethylene glycol units and from 12 to 24 carbon atoms in the f-atty acid.

The superior new asphalt emulsions of the invention possess remarkabiy 10W viscosities compared to similar emulsions whch do not contain the polyglycol ester of fatty acid. The emulsions are characterized by surprisingly high residues considering the 10W viscosities. These important properties permit the most efiective utilization of the emulsions in coating and impregnating applications. The emulsions also have excellent stability under storage conditions and do not increase unduly in viscosity or separate on standing. 'l'heir dernulsbility and quick breaking properties are also outstanding.

According to the present invention, suitable anionic asphalt emulsions are prepared by mixing hot molten asphalt with a hot aqueous solution of an alkali metal hydroxide having a concentration the range of from about 0.01 to about 2.0 percent by weight alkali metal hydroxide. For present purposes, potassium hydroxide, particularly in concentrations of 0.05 to 0.30, is preferred. Usually from 40 to of asphalt is employed with from 20 to 60% of water.

The polyethylene glycol monoester of fatty acid is employed in the auionic asphalt emulsion of the invention in any proportion sufficient to lower the viscosity of the emulsion. Preferably trom about 0.05 to about 2.0 percent by weight is used based on the total emulsion. The polyglycol ester of fatty acid may be added to either the aqueous metal hydroxide solution or the asphalt prior to mixing. It may also be added to the anionic asphalt emulsions atter they are formed. I-Iowever, the most efective reduction in Viscosity is obtained by adding the polyglycol ester of fatty acid to the aqueous alliali metal hydroxide solution prior to mixing with the asphalt.

Suitable polyglycol esters of fatty acids contain from 2 to 75 ethylene glycol units and from 12 to 24 carbon atoms in the fatty acid, as mentoned above. They are illustrated by the formula wherein 11 is the number of glycol units and R is the aliphatic hydrocarbon group of the fatty acid. The fatty acids are either saturated or unsaturated with saturated acids being presently preferred. Illustrative polyethylene glycol esters of fatty acids include polyethylene glycol laurate having 5 ethylene glycol units, polyethylene glyco1 palmitate having 30 ethylene glycol units, polyethylene glycol myristate having 20 ethylene glycol units, polyethylene glycol stearate having 50 ethylene glycol units, polyethylene glycol behenate having 65 ethylene g1ycol units and polyethylene giycol erucate having 60 ethylene glycol units. Presently preferred are the polyethylene glycol monoesters of fatty acids containing an average of trom about 15 to 50 ethylene glycol units and from 12 to 18 carbon atoms in the fatty acid.

A wide variety of asphalts are suitable in. the prepara tion of the superior new asphalt emulsion according to this invention. Asphalts which normally contain sufficient high molecular weight carboxylic acids to provide emulsions upon saponification of the acids with aqueous alkali metal hydroxide solutons are preferred. It is possible, however, to increase or decrease the amount of high molecular weight carboxylic acid in the asphalt and provide more 01 less saponified carboxylic acid emulsifyring agent where that is desirable.

In a typical preparation, the aqueous alk-ali metal hydroxide emulsifying base is mixed with the asphalt at a temperature in the range of frorn about to F. Where colloid mills are employed the temperatures may be raised to 300" F. or more. It is essential that the 3 asphalt be in a molten state prior to miming. Usually, temperatures of around 300 F. are suflicient but the exact temperature will depend on the softening point of the particular asphalt employed in preparing the emuls1on.

In a further illustration of the greatiy improved high residue anionic asphalt emulsious of the invention, a series of emulsions was prepared and tested, as outlined in the following paragraphs.

A11 of the emulsions were prepared in 2,500 gm. quantities in a steam heated, stainless steel vessel equipped with a 1,725 r.p.m. stirrer, temperature gauge, condenser and electrically heated asphalt reservoir. The aqueous test determines the percent by weight of residue which remai-ns after a 25 gm. sample of the emulsion is heated until all of the water is evaporated. The polyethylene glycol monoester of fatty acid employed in the test illus trates two types of esters. One type is the polyethylene glycol stearate having approximateiy 5 ethylene glycol units. This material is known to the trade by the name Ethofat 60/15" and is manufactured by Armour Company. The second type is polyethylene g1ycol stearate having an average of approxirnately 50 ethylene glycol units. This latter material is known to the trade as Ethofat 60/60 and is also manufactured by Armour Company.

Table Properties Variable components Polyglycol ester of Particle size (1!) Storage stability fatty acid, percent Demulsr- 1 week at 160F.

Viscosrty bi1ity Residue, SSF at (0.02 N percent 122F. Calz) Predomi- Demulsi- Range nant Viscosity bility, percent 0.00 226 97 57 6 1-10 2. 442 100 0. 025 469 98 57. 2 110 3 449 100 0.05 656 98 57.2 1 7 2.5 233 98 0. 075 486 98 57. 2 1- 7 2. 5 83 96 0. 10 718 100 56. 8 1-12 3. 5 168 97 0. 451 98 57. 2 1-10 3 108 75 0. 244 99 57. 2 1-10 4 46 84 0. 50 335 100 57. 2 1-10 4 59 61 0. 65 261 100 57. 6 1-10 4 95 52 0. 259 99 57. 6 1 8 4 110 54 1. 00 259 58.0 1-15 4 61 38 280 57.2 1 8 4 432 96 220 100 57. 2 1- 7 3 95 38 85 56.8 0. 5 3 1. 5 30 86 29 63 57.2 0. 5 2 1. 5 24 59 19 59 56.4 0. 5- 2 1 19 57 11 71 56.8 0. 5 7 1 14 67 11 86 56.8 0. 5 8 2 13 83 11 91 57. 2 0. 515 3 14 89 11 91 57. 2 05-15 4 14 88 10 94 57. 2 0. 5-20 4 14 84 10 91 57.2 0 5-20 5 14 60 0.30 711 100 56. 4 1- 5 2 247 100 0.27 27 100 58.4 1 5 2 19 94 0. 24 88 100 57. 6 110 3 33 80 0. 21 71 96 57. 2 %10 1 28 68 0. 18 44 73 57. 6 Vg-1O 1 23 48 0. 15 20 58 56. 8 1 2 2 1 17 47 0. 12 16 68 56. 8 V -1O 1 18 65 0.09 17 73 57. 6 2- 5 1. 5 17 71 0.06 15 88 56. 4 7 4 16 85 0.03 14 70 55. 3 %15 1 15 69 0.00 14 81 65.4 1 5 2 16 82 1 Polyethylene g1yco1 monostearate haviug an average of approximately 5 ethylene g1yco1 units. Polyethyleue g1yco1 monostearate having 2m average of approximately 50 ethyleue g1yco1 units.

NOTE.II1 the above eompositions the KOH concentration was constant at 0.155%.

phase consisting of distilled water, alka1i metal hydroxide and the speeified polyethylene glycol ester of fatty acid is made up in the vessel and brought to a temperature of F. with continuous stirring. Sirnultaneously, the asphalt is put into the asphalt reservoir and brought to a temperature of 250" F. When both the aqueous and asphait phases are at the desired temperatures, the asphalt is added to the aqueous phase over a three-minute period. Following an additional 30 seconds stirring period, the emulsion is withdravm into a one-gallon glass ja1'. The glass jar is covered and piaced in a 120" F. oven for over-night storage prior to testing.

The asphalt ernp1oyed in the tests was a typical Venezuelan asphalt of 200 to 250 penetration. The emulsions were formulated with 58% by weight asphalt, potassium hydroxide, polyethylene glycol ester of fatty acid and the balance water, as indicated in the table below.

The viscosity in seconds Saybolt Furo1 for 60 mis. at 122 F. and the demulsibility were determined according to the Standard Methods of Testng Emuls-ified Asphalts ASTM designation D-244-55. The demulsibiiity of a particular emulsion is the percentage by weight of the asphalt present that fai1s to pass a No. 14 wire cloth when a 100 gin. sample of the emulsion is mixed with 35 mls. of 0.02 N calcium chloride solution. The residue The above test results show that the surprisingly improved anionic asphalt emulsions containing polyglycol esters of fatty acids in accordance with the invention have rnuch lower viscosties than corresponding emulsions which contain no polyglycol esters of fatty acids. This fact is particularly apparent in the stable viscosities of the emulsions after one week in storage at 160 F. The outstandng qualities of asphalt emulsions containing the preferred polyglycol monoesters of: fatty acid are also readily seen from the test results. The esters containing a hgher proportion of ethylene glycol units, as illustrated by the polyglycol ester of fatty acid (2) provide asphalt emulsions with surprisingly 10W viscosities.

The emulsions according to the present invention are also shown by the above test results to have remarkably high residues, considerng their 10W viscosities. The combination of high residues with 10W viscosity means that the emulsions of the nvention are outstandingly ef1ective in coating and impregnating applications.

In further illustration of the superior new anionic asphalt emulsions of the invention, the above test data relating to the polyethylene glycol monostearate having an average of approxirnately 50 ethylene glycol units have been plotted to give the graph of the accornpanying drawing. The graph provides a visual appreciation of the eiect of the polyglycol esters of fatty acds on typica1 anionic asphalt emulsions. When employed in the specific proportons accordng to the present invention a remarkable improvement in viscosity of the asphalt emulsions is obtained by the use of polyglycol ester of fatty accid. The graph further shows that the improved anionic asphalt emulsions not only have desirable 10W viscosities, but a1so possess excellent demulsibility characteristics.

We claim:

1. An mproved high residue asphalt emulsion of 10W vscosity consisting essentially of an anionic soap asphalt emulsion and from 0.05 to 1.0 percent by weight of polyethylene glyco1 monostearate having an average of approximately 50 ethylene glycol units, said monostearate being suficient to lower the viscosity of the emulsion and said anionc soap asphalt emulsion being prepared by mxing from 40 to 80 percent by weight of molten asphalt with from 20 to 60 percent by weight of aqueous solution of frorn about 0.05 te about 0.30 percent by weight of potassium hydroxide so as to saponfy high molecular weight carboxylic acids in the asphalt, the aforesaid proportions being based on the total asphalt emulsion.

2. An improved high residue asphalt emulsion of 10W viscosity consistng essentially of an anionic soap asphalt References Cited in the file of this patent UNITED STATES PATENTS 1.643,675 Montgomerie Sept. 27, 1927 2635055 Figdor Apr. 14, 1953 2,701,777 Farris Feb. 8, 1955 2,706688 Sommer et al. Apr. 19, 1955 2789917 Hardman et al Apr. 23, 1957 OTHER REFERENCES Grifin: The American Perfumer and Essental Oil Review, May 1955, pp. 26-29.

Atlas Guide to the Use of Sorbital and Surfactants in Cosmetcs, pub1. by Atlas Powder Co. 1956, pp. 16, 31. 

1. AN IMPROVED HIGH RESIDUE ASPHALT EMULSION OF LOW VISCOSITY CONSISTING ESSENTIALLY OF AN ANIONIC SOAP ASPHALT EMULSION AND FROM 0.05 TO 1.0 PERCENT BY WEIGHT OF POLYETHYLENE GLYCOL MONOSTEARATE HAVING AN AVERAGE OF APPROXIMATELY 50 ETHYLENE GLYCOL UNITS, SAID MONOSTEARATE BEING SUFFICIENT TO LOWER THE VISCOSITY OF THE EMULSION AND SAID ANIONIC SOAP ASPHALT EMULSION BEING PREPARED BY MIXING FROM 40 TO 80 PERCENT BY WEIGHT OF MOLTEN ASPHALT WITH FROM ABOUT 20 TO 60 PERCENT BY WEIGHT OF AQUEOUS SOLUTION OF FROM ABOUT 0.05 TO ABOUT 0.30 PERCENT BY WEIGHT OF POTASSIUM HYDROXIDE SO AS TO SAPONIFY HIGH MOLECULAR WEIGHT CARBOXYLIC ACIDS IN THE ASPHALT, THE AFORESAID PROPORTIONS BEING BASED ON THE TOTAL ASPHALT EMULSION. 